Imidomethyl derivatives of 1,3,3-trimethylindolino-spiropyran

ABSTRACT

Novel imidomethyl or amidomethyl derivatives of 1,3,3trimethylindolino-spiropyran are produced by reacting a 1,3,3trimethylindolino-spiropyran derivative with an imidomethylating or amidomethylating agent in the presence of a condensing agent and optionally in a solvent. These novel compounds are adapted to be used as a coloring matter for pressure sensitive copy papers and particularly as one component of a coloring matter for black pressure sensitive copy papers.

United States Patent Koga et a1.

[ 1 June 20, 1972 [54] IMIDOMETHYL DERIVATIVES OF1,3,3-TRIMETHYLINDOLINO- SPIROPYRAN [72] Inventors: Kolchl Koga,Toyonaka; Mlnoru llatorl, Takarazuka; Takashl Akamatsu, Ashiya,

all of Japan [73] Assignee: Sumltomo Chemical Company, Ltd.,

Higashi-ku, Osaka, Japan [22] Filed: May 28,1970

[2]] App]. No.: 41,584

[52] US. Cl. ..260/326 D, 117/368, 260/281,

260/326 N, 260/326.11, 282/28 [51] Int. Cl. ..C07d 27/38 [58] Field ofSearch ..260/326 D, 326 N [56] References Cited UNITED STATES PATENTS3,100,778 8/1963 Berman ..260/326.ll

Primary Examiner-Henry R. Jiles Assistant Evaminer-Joscph A. NarcavageAttorney-Stevens, Davis, Miller & Moshcr [5 7] ABSTRACT 11 Claims, NoDrawings IMIDOMETI-IYL DERIVATIVES OF 1,3,3-TRIMETIIYLINDOLINO-SPIROPYRAN The present invention relates to novelimidomethyl or amidomethyl derivatives of1,3,3-trimethylindolinobenzospiropyran (I) orl,3,3-trimethylindolino-[3- naphthospiropyran (ll) represented by thegeneral formula,

CH3 CH3 wherein X and Y represent hydrogen atoms; halogen atoms such aschlorine and bromine atoms; lower alkyl groups such as methyl, ethyl,propyl and butyl groups; lower alkoxy groups such as methoxy and ethoxygroups; phenyl groups; phenoxy groups; benzyl groups or nitro groups; 2represents phthalimidomethyl or a substituted phthalimidomethyl group;maleimidomethyl or a substituted maleimidomethyl group;succinimidomethyl or a substituted succinimidomethyl group;tetrahydrophthalimidomethyl or a substituted tetrahydrophthalimidomethylgroup; glutarimidomethyl or a substituted glutarimidomethyl group; orglutaconimidomethyl or a substituted glutaconimidomethyl group (thesubstituents being amino, nitro, hydroxyl or alkyl groups or halogenatoms) or a group of CH,NHCOR wherein R represents hydrogen atom or analkyl, an alkenyl, an alkynyl, phenyl or a substituted phenyl, benzyl ora substituted benzyl, or phenethyl or a substituted phenethyl group (thesubstituents being amino, nitro, hydroxyl, alkyl or alkoxy groups orhalogen atoms), and n is 1 to 2.

The present invention also relates to a process for producing thesederivatives and pressure sensitive copy papers using these derivativesas pressure sensitive coloring matters.

ln the present invention, the alkyl, alkoxy, alkenyl and alkynyl meanthose having up to five carbon atoms.

Recently so-called no carbon papers or pressure sensitive copy papershave appeared on the market. Previous oily carbon papers have defectsthat, for example, they must be placed between slips and that they areapt to stain clothes or hands. Pressure sensitive copy papers have beennoted as copy papers which obviate the defects and make a contributionto the speed-up of ofiice work.

The coloring matters of the present invention show a shade from yellowto red after color development, and may be used not only as materialsfor red pressure sensitive copy papers but also as one component of thematerials for black pressure sensitive copy papers. The black pressuresensitive copy papers are characterized in that the type-written copypapers can be further easily reproduced in contrast with blue pressuresensitive papers.

Thus, the imidomethylor amidomethyl-l,3,3-trimethylindolino-spiropyrancompounds (I) and (II) according to the present invention may be onecomponent of the coloring mat- .ters for black pressure sensitive copypapers. When they are used alone, they show visible absorption at 450500 p. (in glacial acetic acid) and are developed into a shade fromyellow to red.

The imidomethylor amidomethyl-l ,3,3-trimethylindolinospiropyranderivatives are applied onto the back of paper alone or in admixturewith other suitable coloring matters for pressure sensitive copy papers,and an acid electron adsorbing material such as kaoline or bentonite isapplied onto the surface of other paper. lf such papers are put uponeach other and pressure or shock is applied by pencil or typewriter,both materials are contacted with each other and the colorless coloringmatters are developed to give a colored image.

The compounds of the present invention represented by the formulas (l)and (II) are very rapid in development and give 5 an image of yellow tored having a high density and may be advantageously used in the blendingof coloring matters owing to their broad width of visible absorption.

Thus, the present invention is to provide the imidomethyl or amidomethylderivative of 1,3,3-trimethylindoIino-spiropyran represented by thefonnula (l) and (Il), and a process for the production of the same whichcomprises reacting 1,3,3- trimethylindolino-spiropyran represented bythe formula,

CH: CH; x

N/ O lIIa or CH: CH: Y X

( II-I3 ingformulas:

CHa CH3 GHQ l X CH2+Y T Ha (III) (IV) CH CH3 Y X o CH: CH: CHO

OH X l CH2+ N/ 1 Y CH3 (III) CH3 CHI l 0p \7 CH3 (VII) In the aboveformulas, X and Y are as defined above.

Preferred organic solvents include alcohols such as methanol, ethanoland ethylene glycol; ethers such as dimethyl ether and dioxane; aromatichydrocarbons such as benzene and toluene; and dimethylformamide anddimethyl sulfoxide.

The imidomethyland amidomethyl-l,3,3-trimethylindolino-spiropyran (I)and (II) of the present invention may be easily produced byimidomethylating or amidomethylating the above-mentionedl,3,3-trimethylindolino-B- naphthospiropyran (VI) andl,3,3-trimethylindolino-benzospiropyran (VII), respectively, in thepresence of a condensing agelnt, if necessary in a solvent as shown inthe following formu as:

CH3 CH3 X Y nZ-OH l on3 (VII) cm 0113 1 X (z)n CH3 CH3 Y X nZ-OH 7 t CH3CH3 g l O m \N 7 C'H,

In the above formulas, X, Y, n and Z are as defined above.

The exemplary dicarboxyimide derivatives which may be used as animidomethylating agent in the present invention includeN-methylol-phthalimide, N-methylol-3-nitrophthalimide,N-methylol-4-nitrophthalimide, N-methylol-3-chlorophthalimide,N-methylol4-chlorophthalimide, N-methylol-3,4-dichlorophthalimide,N-methylol-4,S-dichlorophthalimide, N-methylol-3,S-dichlorophthalimide,N-methylol-3,6-dichlorophthalimide, N-methylol-4,5-dibromophthalimide,Nmethylol-3,4-dibromophthalimide, N-methylol-2,3-dibromophthalimide,N-methylol-3-methylphthalimide, N-methylol-4-methylphthalimide,N-methylol-3-methoxyphthalimide, N-methylol-4-methoxyphthalimide,N-methylol-3aminophthalimide, N-methylol-4-aminophthalimide,

N-methylol-3-hydroxyphthalimide, N-methylol-4-hydroxyphthalimide,N-methylol-3,4-dihydroxyphthalimide,N-methylol-3,S-dihydroxyphthalimide,

N-methylol-3 ,o-dihydroxyphthalimide,

N-methylol-4,S-dihydroxyphthalimide,

N-methylol-3,4-dimethylphthalimide,

N-methylol-3,S-dimethylphthalimide,

N-methylol-3,6-dimethylphthalimide,

N-methylol-4,5-dimethylphthalimide,

N-methylol-3,4-dimethoxyphthalimide,

N-methylol-3,S-dimethoxyphthalimide,

N-methylol-3,6-dimethoxyphthalimide,

N-methylol-4,S-dimethoxyphthalimide,

N-methylol-3,4-diaminophthalimide,

N-methylol-3,S-diaminophthalimide,

N-methylol-3,6-diaminophthalimide,

N-methylol-4,5-diaminophthalimide,

N-m ethylol-3 ,4,5 ,6-tetrahydrophthalimide,

N-methylol-l ,2,3 ,4-tetrahydrophthalimide,

N-methylol-maleimide,

N-methylol-dimethylmaleimide,

N-methylol-methylethylmaleimide,

N-methylol-methylpropylmaleimide,

N-methylol-succinimide,

N-methylol-2-phenylsuccinimide,

N-methylol-glutarimide and N-methylol-glutaconimide.

Also, in addition to such N-methylol compounds of dicarboxyimides,N-halomethyl compounds may be used as an imidomethylating agent. Thesecompounds can be easily obtained either by reacting the correspondingdicarboxyimides with formaldehyde to produce N-methylol compoundsaccording to a usual method or by further reacting the N- methylolcompounds thus obtained with a dihalomethyl ether to produceN-halomethyl derivatives.

As the amidomethylating agent, N-methylolamide, N-

chloromethylamides and N-bromomethylamides can be used which arerepresented by the formulas, RCONl-lCl-hOI-I, RCONI-ICI-I,Cl orRCONHCH,B|' wherein R is as defined above.

The N-methylolamides which may be used as an amidomethylating agent inthe present invention include, for example,

N-methylol-formamide N-methylol-acetamide N-methylol-chloracetamideN-methylol-trichloracetamide N-methylol-phenylacetamideN-rnethylol-2-phenyl-propionamide N-methylol-isovaleramideN-methylol-benzamide N-methylol-o-nitrobenzamideN-methylol-m-nitrobenzamide N-methylol-p-nitrobenzamideN-methylol-o-hydroxy-benzamide N-methylol-m-hydroxy-benzamideN-methylol-p-hydroxy-benzamide N-methylol-p-methyl-benzamideN-methylol-o-methyl-benzamide N-methylol-m-methyl-benzamideN-methylol-acrylamide N-methylol-crotonamide N-methylol-propiolamideN-methylol-cinnamamide N-methylol-a-methylacrylamideN-methylol-o-methoxybenzamide N-methylol-m-methoxybenzamideN-methylol-p-methoxybenzamide N-methylol-o-chlorobenzamideN-methylol-m-chlorobenzamide N-methylol-p-chlorobenzamideN-methylol-(o-chlorophenyl) acetamide N-methylol-(m-chlorophenyl)acetamide N-methylol-(p-chlorophenyl) acetamideN-methylol-(o-nitrophenyl) acetamide N-methylol- (m-nitrophenyl)acetamide N-methylol-(p-nitrophenyl) acetamideN-methylol-(o-methoxyphenyl) acetamide N-methylol-(m-methoxyphenyl)acetamide N-methylol-(p-methoxyphenyl) acetamideN-methylol-2-(o-chlorophenyl)-propionamide N-methylol-2-(m-chlorophenyl)propionamide N-methylol-2-(p-chlorophenyl) propionamideN-methylol-2-(o-methoxyphenyl) propionamideN-methylol-2-(m-methoxyphenyl) propionamideN-methyIol-Z-(p-methoxyphenyl) propionamideN-methylol-2-(o-hydroxyphenyl) propionamideN-methylol-2-(m-hydroxyphenyl) propionamideN-methylol-2-(p-hydroxyphenyl) propionamide N-methylol-2-(o-nitrophenyl)propionamide N-methylol-2-(m-nitrophenyl) propionamideN-methylol-2-(p-nitrophenyl) propionamide These amidomethylating agentscan be easily obtained either by reacting the corresponding amides withformaldehyde to produce N-methylol compounds or by N- halomethylatingthe amides with a dihalomethyl ether according to a usual method.

The condensing agents include sulfuric acid, hydrochloric acid,phsphoric acid, boron trifluoride, zinc chloride, aluminum chloride,hydrogen fluoride, phosphorus pentoxide, phosphorus pentachloride,phosphorus oxychloride and formic acid.

As for the reaction solvents, condensing agents such as sulfuric acidmay also act as a solvent. However, halogen-substituted aromatichydrocarbons such as chlorobenzene and dichlorobenzene; aliphatic andalicyclic hydrocarbons such as hexane and cyclohexane; halogenatedaliphatic hydrocarbons such as chloroethane and dichloroethane; etherssuch as ether and dioxane; nitrobenzene and carbon disulfide may be usedas reaction solvent.

The starting l,3,3-trimethylindo]ino-fi-naphtho-spiropyran derivative(VI) or l,3,3-trimethylindolino-benzo-spiropyran derivative (VII) ismixed with a condensing agent if necessary in a solvent and theimidomethylating or amidomethylating agent is then added thereto in amolar ratio of 1.0 to 2.5.

The reaction temperature and the reaction time depend upon the startingmaterials. The desired compound (l) or (II) can be obtained by heatingthe reaction mixture at 0 to 150 C. for several hours, sometimes for to90 hours.

All of the thus obtained compounds (l) and (ll) are new compounds andsoluble in a variety of organic solvents such as, for example, benzene,xylene, chlorinated biphenyl and the like. If the solution is contactedwith kaolin, bentonite, acid clay or the like inorganic compound, abrilliant shade from yellow to red is produced and the shade is highlystable to air and light. Thus, such characteristics may be suitable fora coloring matter for pressure sensitive copy papers.

Previously known 1,3 ,3-trimethylindolino-benzospiropyran andl,3,3-trimethylindolino-B-naphtho-spiropyran derivatives may be used inpressure sensitive copy papers, but they had a defect that they are poorin fastness to sublimation although their development speed is large andthey give a shade of yellowish orange to red. Therefore, the yellowishorange to red image is apt to migrate to the surface of other paper andstain the surface.

The compounds of the present invention are novel ones which haveobviated the defect and have been remarkably improved with respect totheir sublimableness. Therefore, practically valuable pressure sensitivecopy papers can be produced by the use of the compounds.

Pressure sensitive copy papers may be prepared by using at least onecompounds represented by the formulas (l) and (II) according to theconventional method disclosed in many patents and the other literaturereferences. For example, the above-mentioned imidomethyloramidornethyl-l ,3,3- trimethylindolino-spiropyran compound (I) or (ll)is dissolved in a non-volatile and nonpolar solvent such aschlorobiphenyl, mineral oil, paraffin oil or olive oil.

The solution is added to an aqueous gelatin solution with vigorousstirring to disperse as oil drops 1 10 microns in size. The aqueous gumarabic solution is added to the above obtained emulsion, and the wholesolution is coacervated with the pH adjustment or the dilution. The oildrops coated by the coacervate are solidified with alums or aldehydessuch as formalin and glutaraldehyde.

The microcapsules can be isolated by filtration, decantation, orcentrifuge filtration.

The microcapsules thus obtained is applied onto paper and then dried toobtain pressure sensitive copy paper.

The thus obtained pressure sensitive copy papers are improved infastness to sublimation. Therefore, the compounds of the presentinvention are useful as an orange coloring matter for pressure sensitivecopy papers, because the conventional orange coloring matters have beenused with inferior fastness to sublimation.

Also, the compounds of the present invention are highly adapted to onecomponent of a black coloring material for pressure sensitive copypapers because, as described above, they are rapid to develop and give ashade having a high density and show a broad width of visibleabsorption.

The following examples are illustrative only of this invention andshould not be construed as limiting the scope thereof, which is properlydelineated in the appended claims.

EXAMPLE 1 To 60 grams of 89 percent sulfuric acid, 4.9 grams (0.0l5 mol)of 1,3,3-trimethylindolino-B-naphtho-spiropyran was added at 8 to 14 C.Then, 4.21 grams (0.023 mol) of N- methylol-phthalimide was added at thesame temperature. The reaction mixture was kept at 20 to 25 C for 48hours. The progress of the reaction was observed by the thin layerchromatography (hereinafter referred to as T.L.C.) of a sample takenfrom the mixture. The mixture was then discharged into 1,000 cc ofwater. The solution was neutralized with a l0 percent caustic sodasolution to separate crystals.

The crystals were recovered by filtration and washed with water toobtain 7.5 grams of a coloring matter which has the following formula,and which has a visible absorption spectrum A 482 my. (in glacial aceticacid). The coloring matter was improved with respect to its sublimationresistance. Thus, it was far less sublimable than the starting 1,3,3-trimethylindolino-fi-naphthospiropyran.

EXAMPLE 2 To 70 grams of 70 percent sulfuric acid 3.2 grams (0.01 mol)of l,3,3-trimethylindolino-B-naphtho-spiropyran was added at 0 to 5 C.Then, 2.0 grams (0.011 mol) of N- methylol-3,4,5,o-tetrahydrophthalimidewas added at the same temperature. The reaction mixture was kept at 20to 25 C. for 48 hours. The progress of the reaction was observed by theT.L.C. of a sample taken from the mixture. The mixture was thendischarged into 1,000 cc of water. The solution was neutralized with a10 percent caustic soda solution to separate crystals.

The crystals were recovered by filtration and washed with water toobtain 6.l grams of a coloring matter having a visible absorptionspectrum k,, 482 my. (in glacial acetic acid).

EXAMPLE 3 To grams of 70 percent sulfuric acid 6.5 grams (0.02 mol) ofl,3,3-trimethylindolino-B-naphtho-spiropyran was added at to C. Then,2.6 grams (0.02 mol) of N- methylol-succinimide was added at the sametemperature. The reaction was kept at 20 to 25 C for 48 hours. Theprogress of the reaction was observed by the T.L.C. of a sample takenfrom the mixture. The mixture was then discharged into 1,000 cc ofwater. The solution was neutralized with a percent caustic soda solutionto separate crystals.

The crystals were recovered by filtration and washed with water toobtain 6.0 grams of a coloring matter having a visible absorptionspectrum A 483 my. (in glacial acetic acid).

EXAMPLE 4 To 25 grams of 70 percent sulfuric acid 1.1 grams (0.025 mol)of l,3,3-trimethyl-5-chloro-indolino-7 '-bromo-B- naphtho-spiropyran wasadded at 0 to 5 C. Then, 0.67 gram (0.025 mol X 1.5) ofN-methylolphthalimide was added at the same temperature. The reactionmixture was kept at to C for 48 hours. The progress of the reaction wasobserved by the T.L.C. of a sample taken from the mixture. The mixturewas then discharged into 1,000 cc of water. The solution was neutralizedwith a 10 percent caustic soda solution to separate crystals.

The crystals were recovered by filtration and washed with water toobtain 1.3 grams of a coloring matter having a visible absorptionspectrum )t 487 my. (in glacial acetic acid).

EXAMPLE 5 To 25 grams of 70 percent sulfuric acid 1.0 grm (0.025 mol) of1,3 ,3-trimethylindolino-7 '-bromo-B-naphtho-spiropyran was added at 0to 5 C. Then, 067 gram of N-methylolphthalimide was added at the sametemperature. The reaction mixture was kept at 20 to 25 C. for 50 hours.The progress of the reaction was observed by the T.L.C. of a sampletaken from the mixture. The mixture was discharged into 1,000 cc ofwater. The solution was neutralized with a 10 percent caustic sodasolution to separate crystals.

The crystals were recovered by filtration and washed with water toobtain 1.0 gram of a coloring matter having a visible absorptionspectrum h 478 mp. (in glacial acetic acid).

EXAMPLE 6 To 25 grams of 70 percent sulfuric acid 0.6 gram of 1,3,3-trimethyl-5-chloro-indolino-B-naphtho-spiropyran was added at 0 to 5 C.Then, 0.4 gram of N-methylol-3,4,5,6-

tetrahydrophthalimide was added at the same temperature.'

The reaction mixture was allowed to stand overnight at 20 to 25 C. Theprogress of the reaction was observed by the T.L.C. of a sample takenfrom the mixture. The mixture was discharged into 1,000 cc of water. Thesolution was neutralized with a 10 percent caustic soda solution toseparate crystals.

The crystals were recovered by filtration and washed with water toobtain 0.9 gram of a coloring matter having a visible absorptionspectrum A 487 mp (in glacial acetic acid).

EXAMPLE 7 To 50 grams of 70 percent sulfuric acid 3.61 grams (0.01 mol)of 1,3,3-trimethyl-5-chloro-indolino-B-naphthospiropyran was added at 0to 5 C. Then, 3.1 grams (0.015 mol) of N-methylol-4-methoxyphthalimidewas added at the same temperature. The reaction mixture was allowed tostand overnight at 20 to 25 C. The progress of the reaction was observedby the T.L.C. of a sample taken from the mixture. The mixture was thendischarged into 1,000 cc of water. The solution was neutralized with a10 percent caustic soda solution to separate crystals. The crystals wererecovered by filtration and washed with water to obtain 6.2 grams of acoloring matter.

EXAMPLE 8 To 50 grams of 70 percent sulfuric acid 3.3 grams (0.01 mol)of l,3,3-trimethylindolino-B-naphtho-spiropyran was added to 0 to 5 C.Then, 3,2 grams (0.015 mol) of N- methylol-4-chlorophthalimide was addedat the same temperature. The reaction mixture was allowed to standovernight at 20 to 25 C. The progress of the reaction was observed bythe T.L.C. of a sample taken from the mixture. The mixture was thendischarged into 1,000 cc of water. The solution was neutralized with a10 percent caustic soda solution to separate crystals. The crystals wererecovered by filtration and washed with water to obtain 5.9 grams of acoloring matter.

EXAMPLE 9 To 50 grams of 70 percent sulfuric acid 4.50 grams (0.01 mol)of 1,3,3-trimethyl-5-nitro-indolino-7'-bromo-B-naphthospiropyran wasadded at 0 to 5 C. Then, 3.33 grams (0.015 mol) ofN-methylol-3-nitrophthalimide was added at the same temperature. Thereaction mixture was allowed to stand overnight at 20 to 25 C. Theprogress of the reaction was observed by the T.L.C. ofa sample takenfrom the mixture. The mixture was discharged into 1,000 cc of water. Thesolution was neutralized with a 10 percent caustic soda solution toseparate crystals. The crystals were recovered by filtration and washedwith water to obtain 6.1 grams of a coloring matter.

EXAMPLE 10 To 50 grams of 70 percent sulfuric acid 4.36 grams (0.01 mol)of l,3,3-trimethyl-5methoxy-indolino7'-bromo-B- naphtho-spiropyran wasadded at 0 to 5 C. Then, 1.9 grams (0.015 mol) of N-methylolmaleinimidewas added at the same temperature. The reaction mixture was allowed tostand overnight at 20 to 25 C. The rpgress of the reaction was observedby the T.L.C. of a sample taken from the mixture. The mixture wasdischarged into 1,000 cc of water. The solution was neutralized with a10 percent caustic soda solution to separate crystals. The crystals wererecovered by filtration and washed with water to obtain 6.3 grams of acoloring matter having a visible absorption spectrum A 483 my. (inglacial acetic acid).

EXAMPLE 1 l Coloring matters similar to that of Example 1 were obtainedby using l,3,3-trimethyl-5-phenyl-indolino-B-naphthospiropyran, 1,3,3-trirnethyl-7-phenyl-indolino-7 '-bromo-B- naphtho-spiropyran, 1,3,3-trimethyl-5-phenoxy-indolino-B- naphtho-spiropyran, 1,3 ,3,5-tetramethyl-idolino-B-naphthospiropyran andl,3,3,7-tetramethyl-indolino-7'-bromo-B- naphtha-spiropyran in place of1,3,3-trimethyl-indolino-finaphtho-spiropyran, and usingN-methylol-3-methylphthalimide, N-methylol-4-nitrophthalimide,N-chloromethyl-3- nitrophthalimide, N-bromomethyl-4-methylphthalimide,N- methylol-4-chloro-phthalimide, N-methylol-4,5-dibromophthalimide,N-methylol-4,5-dichlorophthalimide, N- methy101-3-methoxy-phthalimide,N-methylol-3-aminophthalimide, N-methylol-l,2,3,6-tetrahydrophthalimide, N- methylol-dimethylmaleinimide,N-methylol-methylethylmaleinimide and N-methylol-2-phenylsuccinimide inplace of N-methylolphthalimide in Example 1.

EXAMPLE 12 To 100 grams of anhydrous dioxane 20.3 grams (0.1 mol) ofS-methoxyl ,3 ,3-trimethyl-indolino-fi-naphtho-spiropyran and 5 grams ofanhydrous zinc chloride were added. Then, 36.0 grams (0.15 mol) ofN-bromomethyl-phthalimide was added. The reaction mixture was warmed atC. for about 3 hours. The progress of the reaction was observed by theT.L.C. of a sample taken from the mixture. The mixture was dischargedinto 2,000 cc of water. The separated crystals were recovered byfiltration, washed with water, washed with a 10 percent aqueous sodiumbicarbonate solution and washed with water to obtain 45 grams of acoloring matter.

2, EXAMPLE 13 Similar coloring matters were obtained by using N-chloromethyl-3-methylphthalimide, N-bromomethyl-4- nitrophthalimide,N-chloromethyl-succinimide and N- bromomethyl-maleinimide in place ofN-bromomethylphthalimide, and using1,3,3-trimethyl-7-phenyl-indolinoflnaphtha-spiropyran,1,3,3-trimethyl-7-methoxy-indolino-B- naphtho-spiropyran and1,3,3,5-tetramethyl-indolino-7- chloro-B-naphtho-spiropyran in place of1,3,3-trimethyl-5- methoxy-indolino-B-naphtho-spiropyran in Example 12.

EXAMPLE 14 To 100 grams of 70 percent sulfuric acid 3.57 grams (0.01mol) of l,3,3-trimethyl-5-methoxy-indolino-B-naphthospiropyran was addedat to C. Then, 4.0 grams (0.022 mol) ofN-methylol-3,4,5,tetrahydrophthalimide was added at the sametemperature. The reaction mixture was allowed to stand overnight at 20to 25 C. The progress of the reaction was observed by the T.L.C. of asample taken from the mixture. The mixture was discharged into 2,000 ccof water. The solution was neutralized with a percent caustic sodasolution to separate crystals. The crystals were recovered by filtrationand washed with water to obtain 7.2 grams of bis(3,4,5,6-tetrahydrophthalimidomethyl l,3,3-trimethyl-5-methoxy-indolino-B-naphtho-spiropyran (n 2).

EXAMPLE 15 To 100 grams of 70 percent sulfuric acid 5.54 grams (0.02mol) of 1,3,3-trimethyl-indolino-benzo-spiropyran was added at 0 to 5 C.Then, 5.32 grams (0.02 mol X 1.5) of N- methylol-phthalimide was addedat the same temperature. The reaction mixture was warmed at to C for 48hours. The progress of the reaction was observed by the T.L.C. of asample taken from the mixture. The mixture was discharged into 1,000grams of water. The solution was neutralized with a 10 percent causticsoda solution to separate crystals. The crystals were recovered byfiltration and washed with water to obtain 8.9 grams of a coloringmatter having a visible absorption spectrum )r,,,,,,= 432 my. (inglacial acetic acid).

EXAMPLE 16 To 25 grams of 70 percent sulfuric acid 1.53 grams (5.0 X 10*mol) of l,3,3-trimethyl-indolino-8 methoxy-benzospiropyran was added at0 to 5 C. Then, 1.0 gram (5 .0 X 10' mol X 1.1) of N-methylolphthalimidewas added at the same temperature. The reaction mixture was kept at 20to 25 C. for 48 hours. The progress of the reaction was observed by theT.L.C. of a sample taken from the mixture. The mixture was dischargedinto 1,000 grams of water. The solution was neutralized with a 10percent caustic soda solution to separate crystals. The crystals wererecovered by filtration and washed with water to obtain 2.3 grams of acoloring matter having a visible absorption spectrum A 400 mu (inglacial acetic acid).

EXAMPLE 1? To 25 grams of 70 percent sulfuric acid 1.5 grams (5 X 10'mol) of l,3,3-trimethyl5-chloro-indolino-benzo-spiropyran was added at 0to 5 C. Then, 1.35 grams (5 X 10* mol X 1.5) of N-methylolphthalimidewas added at the same temperature. The reaction mixture was kept at 20to 25 C. for 24 hours. The progress of the reaction was observed by theT.L.C. of a sample taken from the mixture. The mixture was dischargedinto 500 cc of water. The solution was neutralized with a 10 percentcaustic soda solution to separate crystals. The crystals were recoveredby filtration and washed with water to obtain 2.4 grams of a coloringmatter having a visible absorption spectrum A 438 mp.

0 EXAMPLE 18 To 50 grams of 70 percent sulfuric acid 3.6 grams (0.01mol) of 1,3,3-trimethyl-indolino-6-bromo-benzo-spiropyran was added at 0to 5 C. Then, 1.43 grams (0.011 mol) of N- methylol-succinimide wasadded at the same temperature. The reaction mixture was kept at 20 to 25C for 40 hours. The progress of the reaction was observed by the T.L.C.of a sample taken from the mixture. The mixture was discharged into1,000 grams of water. The solution was neutralized with a 10 percentcaustic soda solution to separate crystals. The crystals were recoveredby filtration and washed with water to obtain 4.3 grams of a coloringmatter.

EXAMPLE 19 To 50 grams of 70 percent sulfuric acid 3.1 grams (0.01 mol)of 1,3,3-trimethyl-7-chloro-indolino-benzo-spiropyran was added at 0 to5 C. Then, 2.0 grams (0.011 mol) of N-methylol-3,4,5,6-tetrahydro-phthalimide was added at the sametemperature. The reaction mixture was allowed to stand overnight at 20to 25 C. The progress of the reaction was observed by the T.L.C. of asample taken from the mixture. The mixture was discharged into 1,000grams of water. The solution was neutralized with a 10 percent causticsoda solution to separate crystals. The crystals were recovered byfiltration and washed with water to obtain 4.8 grams of a coloringmatter.

EXAMPLE 20 To grams of 70 percent sulfuric acid 3.2 grams (0.01 1 mol)of 1,3,3,7tetramethyl-indolino-benzo-spiropyran was added at 0 to 5 C.Then, 3.9 grams (0.022 mol) of N- methylophthalimide was added at thesame temperature. The reaction mixture was allowed to stand overnight at20 to 25 C. The progress of the reaction was observed by the T.L.C. of asample taken from the mixture. The mixture was discharged into 2,000 ccof water. The solution was neutralized with a 10 percent caustic sodasolution to separate crystals. The crystals were recovered by filtrationand washed with water to obtain 6.7 grams ofbis-(phthalimidomethyl)-l,3,3,7-tetramethyl-indolino-benzo-spiropyran (n2).

EXAMPLE 21 To 50 grams of 70 percent sulfuric acid 3.5 grams (0.01 mol)of l,3,3-trimethyl-indolino-5'-phenyl-benzo-spiropyran was added at 0 to50 C. Then, 3.33 grams (0.015 mol) of N- methylol-3-nitrophthalimide wasadded at the same temperature. The reaction mixture was allowed to standovernight at 20 to 25 C. The progress of the reaction was observed bythe T.L.C. of a sample taken from the mixture. The mixture wasdischarged into 1,000 grams of water. The solution was neutralized witha 10 percent caustic soda solution to separate crystals. The crystalswere recovered by filtration and washed with water to obtain 5.7 gramsof a coloring matter.

EXAMPLE 22 Coloring matters similar to that of Example 15 were obtainedby using l,3,3-trimethy1-S-phenyl-indolino-benzospiropyran, 1,3,3-trimethy1-7-phenyl-indo1ino-5 bromobenzo-spiropyran,1,3,3-trimethyl-5-phenoxy-indolinobenzo-spiropyran, 1,3 ,3,5-tetramethyl-indolino-benzospiropyran and1,3,3,7-tetramethyl-indolino-5'-chlor0-benzospiropyran in place of1,3,3-trimethylindolinobenzospiropyran, and usingN-methylol-3-methylphthalimide, N- methylol-4-nitrophthalimide,N-chloromethyl-3-nitrophthalimide, N-bromomethyl-4-methylphthalimide,N-methylol-4- chlorophthalimide, N-methylol-4,5-dibromophthalimide, N-methylol-4.S-dichlorophthalimide, N-methylol-3-methoxyphthalimide,N-methylol-3-aminophthalimide, N-methyloll,2,3,o-tetrahydrophthalimide,N-methylol-dimethylmaleinimide and N-methylol-Z-phenyl-succinimide inplace of N- methylol-phthalimide in Example 15.

uunu

1.1. EXAMPLE 23 To 70 grams of 70 percent sulfuric acid 4.9 grams of1,3,3- trimethylindolino-B-naphtho-spiropyran was added at to C. Then,3.0 grams (1.5 molar ratio) of N-methylol-benzamide was added at thesame temperature. .If it was observed that there were no lumps, thereaction mixture was kept at 20 to 25 C. for 15 hours. The disappearanceof the starting materials was confirmed by the T.L.C. of a sample takenfrom the mixture. The mixture was discharged into 1,000 grams of icewater. The solution was neutralized with percent caustic soda at 20 to25 C. to separate crystals. The thus separated crystals were recoveredby filtration and washed with water to obtain 7.6 grams of a coloringmatter having a visible absorption spectrum )t 483 m (in glacial aceticacid).

This coloring matter is remarkably superior in sublimation resistance tothe starting 1,3,3-trimethylindolino-B-naphthospiropyran.

EXAMPLE 24 Into 70 grams of 70 percent sulfuric acid 3.2 grams of 1,3,3-trimethylindolino-B-naphtho-spiropyran was charged at 0 to 5 C. Then,098 gram 1.1 mol) of N-methylol-acetamide was added at the sametemperature. The reaction mixture was kept at 20 to 25 C. for 10 hours.The mixture was discharged into 1,000 grams of ice water. The solutionwas neutralized with a 10 percent caustic soda solution to separatecrystals. The crystals were recovered by filtration and washed withwater to obtain 6.1 grams of a coloring matter having a visibleabsorption spectrum k 482 my. (in glacial acetic acid).

EXAMPLE 25 To 50 grams of 70 percent sulfuric acid 3.1 grams (0.01 mol)of 1,3 ,3-trimethylindolino-8 -methoxybenzo-spiropyran was added at 0 to5 C. Then, 2.2 grams (0.01 X 1.1 mol) of N-methylol-p-nitrobenzamide wasadded at the same temperature. The reaction mixture was kept at 20 to 25C. for 48 hours. The mixture was discharged into 1,000 grams of icewater. The solution was neutralized with a 10 percent caustic sodasolution to separate crystals. The crystals were recovered by filtrationand washed with water to obtain 5.1 grams of a coloring matter having avisible absorption spectrum A 399 my. (in glacial acetic acid).

EXAMPLE 26 To 50 grams of 70 percent sulfuric acid 3.1 grams of 1,3,3-trimethyl-7-chloro-indolino-benzo-spiropyran was added at 0 to 5 C.Then, 2.1 grams (1.1 mol) of N-methyloltrichloroacetamide was added atthe same temperature. The

reaction mixture was allowed to stand overnight at 20 to 25 C. Themixture was discharged into 1,000 grams of ice water. The solution wasneutralized with a 10 percent caustic soda solution to separatecrystals. The crystals were recovered by filtration and washed withwater to obtain 5.0 grams of a coloring matter having a visibleabsorption spectrum A 439 my. (in glacial acetic acid).

EXAMPLE 27 12. EXAMPLE 28 Into 70 grams of 70 percent sulfuric acid 3.6grams of 5- chloro-l ,3,3-trimethylindolino-B-naphtho-spiropyran wascharged at 0 to 5 C. Then, 1.8 grams (1.1 mol) of N-methylol-p-toluamide was added at the same temperature. The reactionmixture was allowed to stand at to C. for 12 hours. The mixture wasdischarged into 1,000 grams of ice water. The solution was neutralizedwith a 10 percent caustic soda solution to separate crystals. Thecrystals were recovered by filtration and washed with water to obtain5.1 grams of a coloring matter having a visible absorption spectrum A493 my. (in glacial acetic acid).

EXAMPLE 29 Into 70 grams of 70 percent sulfuric acid 3.8 grams of 5chloro-1,3,3-trimethylindolin0-6'-phenyl-benzo spiropyran I was chargedat 0 to 5 C.'Then, 1.8 grams (1.1 mol) of N- methylol-phenyl-acetamidewas added at the same temperature. The reaction mixture was kept at 20to 25 C. for 10 hours. The mixture was discharged into 1,000 grams ofince water. The solution was neutralized with a 10 percent caustic sodasolution to separate crystals. The crystals were recovered by filtrationand washed with water to obtain 5.5 grams of a coloring matter having avisible absorption spectrum A 460 my. (in glacial acetic acid).

EXAMPLE 30 Coloring matters similar to that of Example 23 were obtainedby using 5 -methoxy-1 ,3 ,3 -trimethylindolino-B-naphtho-spiropyran7-bromo-1,3,3-trimethylindolino-B-naphtho-spiropyran 5-phenyl-1,3,3-trimethylindolino-B-naphtho-spiropyran 1,3,3,5-tetramethylindolino-fl-naphtho-spiropyran 1,3,3 ,7-tetramethylindolino-B-naphtho-spiropyran 1 ,3 ,3-trimethylindolino-7-chloro-B-naphtho-spiropyran 1,3 ,3-trimethylindolino-7'-methoxy-B-naphtho-spiropyran 1,3 ,3 -trimethylindolino-7'-nitro-fi-naphtho-spiropyran S-methoxy-l ,3 ,3 -trimethylindolino-7-bromo-B-naphthospiropyran 5-chloro-1,3 ,3-trimethylindolino-7'-chloro-B-naphthospiropyran S-bromol ,3,3-trimethylindolino-7'-bromo-B-naphthospiropyran 7-phenyl-l ,3 ,3-trimethylindolino-7-chloro-B-naphthospiropyran S-methoxy-l ,3 ,3-trimethylindolino-benzo-spiropyran 5 -choro-1,3,3-trimethylindolino-benzo-spiropyran 7-chloro-1,3,3-trimethylindolino-benzo-spiropyran 5-bromo-1,3,3-trimethylindolino-benzo-spiropyran 7-phenyl-1,3,3-trimethylindolinobenzo-spiropyran 1,3,3,5-tetramethylindolino-benzo-spiropyran 1,3,3,7-tetramethylindolino-benzo-spiropyran 1,3,3-trimethylindolino-6'-bromo-benzo-spiropyran l,3,3-trimethylindolino-6'-methoxy-benzo-spiropyran 1,3 ,3-trimethylindolino-6-nitro-benzo-spiropyran 1,3 ,3-trimethylindolino-6'-chloro-benzo-spiropy ran 1,3 ,3-trimethylindolino-8'-chloro-benzo-spiropyran 1,3 ,3-trimethylindolino-8-bromo-benzo-spiropy ran 1,3 ,3-trimethylindolino-8'-nitro-benzo-spiropyran S-methoxy-l,3,3-trimethylindolino-8'-methoxy-spiropyran5-methoxy-1,3,3-trimethylindolino-6'-chloro-spiropyran S-methoxy-l,3,3-trimethylindolino-6-bromo-benzospiropyran S-bromol ,3,3-trimethylindolino-6 '-bromo-benzospiropyran S-chloro- 1,3,3-trimethylindolino-8 '-methoxy-benzospiropyran 7-bromo-1,3,3-trimethylindolino-6 '-methoxy-benzospiropyran and 5 -phenyl-1,3,3-trimethylindolino-8 '-methoxy-benzo' spiropyran in place ofl,3,3-trimethylindolino-fl-naphtho-spiropyran, and usingNemethylol-p-chloro-benzamide, N-methylol-p-aminobenzamide andN-methylol-a-chloro-acetamide in place of N- methylolbenzamide inExample 23.

EXAMPLE 31 5.0 grams of phthalimidomethyl-l ,3,3-tri-methylindolino-B-naphtho-spiropyran was dissolved in M grams of dichlorodiphenyl. Thesolution was added to 60 grams of 10.0 percent aqueous gelatin solutionand dispersed as oil drops of about microns to microns in size withvigorous stirring. The emulsion was mixed with 60 grams of 10 aqueousgum arabic solution and adjusted the pH-value to 4.8 with acetic acidsolution. Thus the coacervation with gelatin and gum arabic wasfinished. The wall around the droplet was then solidified by treating itwith grams of 30 percent formalin and a 10 percent sodium hydroxidesolution was added to adjust the pH value to 9.0 on cooling. Afterstirring for 30 minutes, the obtained mixture was warmed at the speed of1.0" C. per minute. The solidification was finished at 50 C. Thusobtained capsules were isolated by the decantation or filtration, thenapplied onto paper with proper carriers such as paste. The amount of thecapsules applied was about 8.0 grams per in of paper. When the paper wasput upon a paper coated with an electron adsorbing material such asactivated clay or kaolin and pressure was applied thereto, an orange redimage of a high density was immediately obtained. The development timewas short and the sublimation fastness and light fastness of the imagewere excellent.

EXAMPLE 32 5.0 grams of3,4,5,6-tetrahydro-phthalimido-methyl-indolino-B-naphto-spiropyran wasdissolved in 150 grams of olive oil. The solution was added to 60 gramsof 10.0 percent aqueous gelatin solution and dispersed as oil drops of 3microns to 5 microns in size with vigorous stirring. The emulsion wasmixed with 60 grams of 10 percent agar solution and adjusted thepl-l-value to 4.5 with acetic acid. The drops coated by the coacervatedlayer of gelatin and agar were hardened with 30 grams of tannic acid orgallic acid. After solidification was ended, the obtained capsules weregot with the decantation and applied onto paper. The pressure sensitivecopy paper was obtained after dried. The amount of the capsules appliedwas about 8 grams per m of the paper. When the paper was put upon apaper coated with an electron adsorbing material such as activated clayor kaolin and pressure was applied thereto, an orange red image of ahigh density was immediately obtained. The development time was shortand the light fastness of the image was excellent.

EXAMPLE 33 0.1 gram of benzamidomethyl-l,3,3-trimethyl-indolino-6'-methoxy-benzospiropyran and 0.2 gram of terephthaloyl chloride weredissolved in 25 grams of dichlorodiphenyl. The above obtained solutionwas mixed with 200 g of 0.5 percent sodium bicarbonate solution anddispersed as oil drops of ca. 1 p. l0 p. in size with vigorous stirring.Well stirring, the emulsion was mixed with 50 grams of 10 percentethylene glycol. The surface polymerization of terephthaloyl chlorideand ethylene glycol made the oil drops of the dye coated with thepolyester film.

The capsules were isolated with the decantation, then applied onto paperwith proper carriers such as paste. The amount of the capsules appliedwas about 8.0 grams per m of paper. When the thus treated paper was putupon a paper coated with an electron adsorbing material such asactivated clay or kaolin and pressure was applied thereto, a yellowishorange image of a high density was obtained. The development time wasshort and the light fastness of the image was excellent.

4. EXAMPLE 34 A solution of 4 g of chloroacetamido-methyl-l,3,3-trimethyl-indolino-7'-bromo-fi-naphtho-spiropyran in grams ofchlorinated biphenyl was added to 60 grams of 10.0 percent aqueousgelatin solution and dispersed as oil drops of about 3 microns to 5microns in size with vigorous stirring. The emulsion was mixed with 60grams of 10.0 percent aqueous gum arabic solution and adjusted thepl-I-value to 4.8 with acetic acid. The wall around the droplet was thensolidified by treating it with 15 grams of 30 percent formalin and a 10percent sodium hydroxide solution was added to adjust the pH value to9.0 on cooling. After stirring for 30 minutes the obtained mixture waswarmed at the speed of 1.0" C per minute.

The solidification was finished at 50 C. Thus obtained capsules wereisolated by the decantation, then applied onto paper with propercarriers such as paste. The amount of the capsules applied was about 8.0grams per m of paper. When the paper was put upon a surface coated withactivated clay and pressure was applied thereto, an orange red image wasproduced.

EXAMPLE 35 Similar pressure sensitive copy papers were obtained by usingthe following compounds in place of benzamidomethyll,3,3-trimethylindolino-6 -methoxy-benzo-spiropyran orchloroacetamidomethyll ,3 ,3 -trimethyl-7 '-bromo-B-naphthospiropyran inExample 33 or 34.

Amidomethyl and imidomethyl derivatives of the following compounds:

S-Methoxy-l ,3 ,3-trimethylindolino-fl-naphtho-spiropyran 5 -B rom ol ,3,3trim ethylindolinofl-naphtho-spiropyran S-Phenyl-l ,3,3-trimethylindolino-B-naphtho-spiropyran S-Nitro-l,3,3-trimethylindolino-B-naphtho-spiropyran l ,3 ,3 ,5-Tetramethylindolino-B-naphtho-spiropyran l ,3,3,7-Tetramethylindolino-fi-naphtho-spiropyran 7-Bromol ,3,3-trimethylindolino-B-naphtho-spiropyran 7-Methoxy-l ,3,3-trimethylindolino-B -naphtho-spiropyran 7-Phenoxy-l,3,3-trimethylindolino-fl-naphtho-spiropyran 7 -Phenyll ,3,3-trimethylindolino-B-naphtho-spiropyran l ,3 ,3-Trimethylindolino-7'-bromo fl-naphtho-spiropyran l ,3 ,3-Trimethylindolino-7-nitro-fl-naphtho-spiropyran S-Methoxyl ,3,3-trimethylindolino-7'-chloro-B-naphthospiropyran S-Methoxy-l ,3 ,3-trimethylindolino-7'-bromo-B-naphthospiropyran 5Methoxy-l ,3,3-trimethylindolino-7-methoxy-B-naphthospiropyran 5 -Bromol ,3 ,3-trimethylindolino-7'-chloro-B-naphthospiropyran S-Bromol ,3 ,3-trimethylindolino-7'-nitro-B-naphthospiropyran S-Bromol ,3 ,3-trimethylindolino-7-methoxy-B-naph thospiropyran S-Chloro-l ,3,3-trimethylindolino-7-bromo-fl-naphthospiropyran 5-Chloro-l ,3,3-trimethylindolino-7'-nitro-fi-naphthospiropyran S-Phenyl-l ,3 ,3-trimethylindolino-7-chloro-fi-naphthospiropyran X S-Phenyl-l ,3 ,3-trimethylindolino-7'-bromo-fl-naphthospiropyran 5 -Phenyl-l ,3 ,3-trimethylindolino-7'-methoxy-fi-naphthospiropyran S-Nitro- 1 ,3,3 -trimethylindolino-7'-chloro-B-naphthospiropyran S-Nitro-l ,3,3 -trimethylindolino-7'-nitro-B-naphthospiropyran S-Nitro-l ,3,3 -trimethylindolino-7-methoxy-B-naphthospiropyran l ,3 ,3,5-Tetramethylindolino-7-bromo-B-naphthospiropyran l ,3 ,3,5-Tetramethylindolino-7'-nitro-B-naphtho-spiropyran 1,3 ,3 ,7-Tetramethylindolino-7-chloro-B-naphthospiropyran 1,3 ,3 7-Tetramethylindolino-7 '-bromo-B-naphthspiropyran 1,3 ,3 ,7-Tetramethylindolino-7'-methoxy-fl-naphthospiropyran 7-Chloro-l ,3 ,3-trimethylindolino-7'-chloro-fl-naphthospiropyran 7-Chlorol ,3 ,3-trim ethylindolino-7-nitro-B-naphth0- spiropyran 7-Chloro-1,3,3rtrimethylindolino-7'-methoxy-B-naphthospiropyran 7-B romol ,3 ,3-trimethylindolino-7'-bromo-B-naphthospiropyran 7-Bromol ,3 ,3-trimethylindolino-7-nitro-}3-naphthospiropyran 7-Methoxy-1 ,3 ,3-trimethylindolino-7-chloro-B-naphthospiropyran 7-Methoxy-1,3,3-trimethylindolino-7'-bromoB-naphthospiropyran 7-Methoxy-l ,3 ,3-trimethylindolino-7-methoxy-B-naphthospiropyran 7-Nitrol ,3 ,3-trimethylindolino-7'-chloro-B -naphthospiropyran 7-Nitrol ,3 ,3-trimethylindolino-7'-nitro-B-naphthospiropyran 7-Nitro-l ,3,3-trimethylindolino-7'-methoxy-B -naphthospiropyran 7-Phenoxy-1,3 ,3-trimethylindolino-7'-nitro-B-naphthospiropyrart 7-Phen oxyl ,3 ,3-trimethylindolino-7'-bromo-B-naphthospiropyran 7-Phenyl-l ,3 ,3-trimethylindolino-7'-chloro-B-naphthospiropyran 7-Pheny1-l ,3 ,3-trimethylindolino-7'-bromo-B-naphthospiropyran 7-Phenyl-l ,3 ,3-trimethylindolino-7'-nitro-B-naphth0- spiropyran 1,3 ,3-Trimethylindolino-benzo-spiropyranS-Nitrol ,3 ,3-trimethylindolino-benzo-spiropyran 5-Phenyl-1,3,3-trimethylindolino-benzo-spiropyran 7-Bromo-1 ,3,3-trimethylindolino-benzo-spiropyran 1,3 ,3,5-Tetramethylindolino-benzo-spiropyran 1,3,3-Trimethylindolino-6'-chloro-benzo-spiropyran 1,3 ,3-Trimethylindolino-6 '-nitro-benzo-spiropyran 1,3 ,3-Trimethylindolino-8 -chloro-benzo-spiropyran S-Methoxy-l,3,3-trimethylindolino-6'-bromo-benzospiropyran S-Methoxy-l,3,3-trimethylindolino-8 -nitro-benzospiropyran S-Methoxy-l ,3,3-trimethylindolino-8 '-bromo-benzospiropyran S-Chloro-l,3,3-trimethylindolino-6 -methoxy-benzospiropyran S-Chloro-l ,3 ,3-trimethylindolino-S '-methoxy-benzospiropyran S-Nitrol,3,3-trimethylindolino-6'-chloro-benzospiropyranS-Nitro-1,3,3-trimethylindolino-6'-methoxy-benzospiropyran S-Nitrol ,3,3-trimethylindolino-8 '-bromo-benzospiropyran 5-Bromo-1,3,3-trimethylindolino-6 '-chloro-benzospiropyran 5-Bromo-1,3,3-trimethylindolino-6 '-nitro-benzo-spiropyran S-Bromo-l,3,3-trimethylindolino-8'-chloro-benzospiropyran 5 -Phenoxy-l ,3 ,3-trimethylindolino-6 -chloro-benzospiropyran S-Phenoxy-l ,3,S-trimethylindolino-B '-nitro-benzospiropyran SPhenoxyl,3,3-trimethyIindolino-8 -bromo-benzospiropyran S-Phenyll ,3,3-trimethylindolino-6-methoxy-benzospiropyran S-Phenyll,3,3-trimethylindolino-8 -methoxybenzospiropyran 7-Methoxy-l ,3,3-trimethylindolino-6'-bromo-benzospiropyran 7-Methoxy-l ,3,3-trimethylindolin0-6'-nitro-benzospiropyran 7-Methoxyl ,3,3-trimethylindolino-8 -chloro-benzospiropyran 7-Chlorol ,3,3-trimethylindolino-6 '-chloro-benzo-v spiropyran 7-Chloro-l,3,3-trimethylindolino-8 '-nitro-benzospiropyran 7-Chlor0-l,3,3-trimethylindolino-8 '-bromo-benzospiropyran 7-Bromo-l ,3,3-trimethylindolino-6 '--methoxy-benzospiropyran 7-Bromo-1,3,3-trimethylindolino-8 -methoxy-benzospiropyran 7-Phenoxy- 1,3 ,3-trimethylindoIino-6 -chloro-benzospiropyran 7-Phenoxyl ,3,3-trimethylindolino-6 -nitro-benzospiropyran 7-Phenoxy-l ,3,3-trimethylindolino-8 '-bromo-benzospiropyran 7-Phenyll,3,3-trimethylindolino-6 '-chloro-benzospiropyran 7-Phenyll ,3,3-trimethylindolino-8 -nitro-benzo-spiropy ran 7-Phenyll ,3,3-trimethylindolino-8 '-chloro-benzospiropyran 1,3 ,3 ,5-Tetramethylindolino-6 '-methoxy-benzo-spiropyran 1,3 ,3,5-Tetramethylindolino-8 -methoxy-benzo-spiropyran l ,3 ,3 ,7-Tetramethylindolino-6'-Chloro-benzo-spiropyran 1,3 ,3 ,7-Tetramethylindolino-6-nitro-benzo-spiropyran 1,3 ,3 ,7-Tetramethylindolino-8 '-chloro-benzo-spiropyran Also, similar pressuresensitive copy papers were obtained by using phthalimidomethylderivatives,

maleimidomethyl derivatives,

succinimidomethyl derivatives,

tetrahydrophthalimidomethyl derivatives,

formamidomethyl derivatives,

acetamidomethyl derivatives,

propionamidomethyl derivatives,

butyramidomethyl derivatives,

acrylamidomethyl derivatives,

benzoamidomethyl derivatives,

phenylacetamidomethyl derivatives, and

propionamidomethyl derivatives of the above-mentioned compounds.

EXAMPLE 36 4 Grams of 3,4,5,6-tetrahydrophthalimido-methyl-l ,3,3,-trimethylindolino-7'-bromo-B-naphtho-spiropyran, 4 grams of2methyl-5-methoxy-4-amino-4',4"-bis-(dimethylaminophenyl)-triphenylmethaneand 3.0 grams of 2-tert.-butyl-4-methyl- 6-diethyl-aminofluorane weredissolved in 160 grams of chlorinated diphenyl. The solution was addedto grams of a 1 1.0 percent gelatin sol and dispersed as oil drops ofabout 3 to 5 p. in size with vigorous stirring.

The emulsion was mixed with 120 grams of 10 percent aqueous gum arabicsolution and adjusted the pH value to 4.8 with acetic acid. Thus thecoacervation with gelatin and gum arabic was finished. The wall aroundthe droplet was then solidified by treating it with 30 grams of 30percent formalin and a 10 percent sodium hydroxide solution was added toadjust the pH value to 9.0 on cooling. After stirring for 30 minutes,the obtained mixture was warmed at the speed of 1.0 C. per minute. Thesolidification was finished at 50 C. Thus obtained capsules wereisolated by the filtration, then applied onto paper to obtain pressuresensitive copy paper with proper carriers such as paste. The amount ofcapsules applied was about 8 grams per m. When the paper was put upon apaper coated with an electron absorbing material such as acid clay orbentonite and pressure was applied thereto by pencil or typewriter, areddish black to black image was obtained.

EXAMPLE 37 2.0 Grams of phthalimidomethyl-'1,3,3-trimethyl-indolino-7-bromo-B-naphtho-spiropyran, 3.0 grams of 1,2-benz-6-diethyIamino-fluorane, 3.0 grams of Crystal Violet lactone and 3.0 gramsof benzoyl leuco Methylene Blue were dissolved in 240 grams ofchlorinated biphenyl.

The emulsion was mixed with 159 grams of percent aqueous gum arabicsolution and adjusted the pH-value to 4.8 with acetic acid. Thus thecoacervation with The wall around the droplet was then solidified bytreating it with 45 grams of 30 percent formalin and a 10 percent sodiumhydroxide solution was added to adjust the pH value to 9.0 on cooling.After stirring for 30 minutes, the obtained mixture was warmed at thespeed of 1.0 C per minute. The solidification was finished at 50 C. Thusobtained capsules were isolated by the decantation, then applied ontopaper to obtain pressure sensitive copy paper with proper carriers suchas paste. The amount of capsules applied was 8.0 grams per m of paper.When the paper was put upon a paper coated with an electron adsorbingmaterial such as acid clay or bentonite and pressure was appliedthereto, a black image was obtained.

What we claim is:

l. A compound of the formula,

CH3 CH wherein X represents hydrogen, halogen, alkyl of 1-5 carbonatoms, alkoxy of one-five carbon atoms, phenoxy, phenyl, benzyl, ornitro; Y represents hydrogen, halogen, alkyl of one-five carbon atoms,alkoxy of one-five carbon atoms, phenyl, benzyl, or nitro; Z representsphthalimidomethyl or a substituted phthalimidomethyl group,tetrahydrophthalimidomethyl or a substituted tetrahydrophthalimidomethylgroup (the substituents being amino, nitro, hydroxyl, alkyl of one-fivecarbon atoms or halogen); and n in l to 2.

2. Phthalimidomethyl-l,3,3-trimethyl-indolino-B-naphthospiropyran.

3.3,4,5,6-Tetrahydr0phthalimidomethyl-l,3,3-trimethylindolino-B-naphtho-spiropyran.

4. Phthalimidomethyl-l ,3,3-trimethyl-5-chloro-indolino-7'-bromo-fi-naphtho-spiropyran.

5. Phthalimidomethyll ,3 ,3-trimethylindolindolino-7bromo-B-naphtho-spiropyran.

6. 3,4,5 ,6-Tetrahydrophthalimido-methyl-1,3,3-trimethyI-5-chloro-indolino-B-naphtho-spiropyran.

7.4-Methoxyphthalimidomethyl-l,3,3-trimethyl-5-chloroindolino-B-naphtho-spiropyran.

8. 4-Chlorophthalimidomethyl-l,3,3-trimethylindolino-B-naphtho-spiropyran.

9. 3-Nitrophthalimidomethyll,3,B-trimthyl-S-nitro-indolino-7'-bromo-B-naphtho-spiropyran.

l0. Phthalimidomethyl-l,3,3-trimethyl-5-methoxy-ind0linofi-naphtho-spiropyran.

ll. -Bis-(3,4,5,6-tetrahydrophthalimidomethyl)trimethyl-5-methoxy-indolino-B-naphtho-spiropyran.

2. Phthalimidomethyl-1,3,3-trimethyl-indolino- Beta -naphtho-spiropyran.3. 3,4,5,6-Tetrahydrophthalimidomethyl-1,3,3-trimethyl-indolino-Beta-naphtho-spiropyran. 4.Phthalimidomethyl-1,3,3-trimethyl-5-chloro-indolino-7''-bromo-Beta-naphtho-spiropyran. 5.Phthalimidomethyl-1,3,3-trimethylindolindolino-7''-bromo- Beta-naphtho-spiropyran. 6.3,4,5,6-Tetrahydrophthalimido-methyl-1,3,3-trimethyl-5-chloro-indolino-Beta -naphtho-spiropyran. 7.4-Methoxyphthalimidomethyl-1,3,3-trimethyl-5-chloro-indolino-Beta-naphtho-spiropyran. 8.4-Chlorophthalimidomethyl-1,3,3-trimethylindolino- Beta-naphtho-spiropyran. 9.3-Nitrophthalimidomethyl-1,3,3-trimethyl-5-nitro-indolino-7''-bromo-Beta -naphtho-spiropyran. 10.Phthalimidomethyl-1,3,3-trimethyl-5-methoxy-indolino Beta-naphtho-spiropyran.
 11. Bis-(3,4,5,6-tetrahydrophthalimidomethyl)1,3,3-trimethyl-5-methoxy-indolino- Beta -naphtho-spiropyran.